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(11) | EP 1 775 735 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Electrical insulation system based on poly (butylene terephthalate) |
| (57) Electrical insulation system based on poly(butylene terephthalate), optionally containing
further additives, wherein said poly(butylene terephthalate) (i) has been obtained
by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate)
resin, contains (ii) at least one filler material or a mixture of such filler materials
in an amount of up to 85% by weight, and (iii) at least one hydrophobic compound or
a mixture of such compounds, preferably an organopolysiloxane, in an amount of 0.1%
to 10% by weight, calculated to the weight of the insulation system; method of making
said electrical insulation systems. |
[0001] The present invention refers to an electrical insulation system based on poly(butylene terephthalate) wherein said poly(butylene terephthalate) has been obtained by polymerising a cyclic (also named macrocyclic) low molecular weight oligomeric poly(butylene terephthalate) resin.
State of the art
[0002] Currently, electrical insulation systems are made of anhydride-cured epoxies. The reason why electrical insulations are widely made from these materials is because they offer a good compromise between cost, electrical, mechanical and thermal properties. Anhydride-cured epoxies, however, present some important drawbacks especially from an environmental point of view. The use of anhydrides is under scrutiny of different authorities and could eventually be banned in the future. Anhydride-cured epoxies also are crack sensitive materials which causes problems in various manufacturing processes.
[0003] It has now been found that poly(butylene terephthalate) when made from a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin can be used as an electrical insulation system and at the same time is an environmentally friendly recyclable material. Its excellent fracture toughness properties shows the potential to decrease the occurrence of defects linked to matrix shrinkage upon cure. This material further offers new manufacturing possibilities which allow a decrease of production cycle time and, due to the non-exothermal polymerization reaction, also offers the possibility of manufacturing bulky parts with limited residual stresses.
[0004] Cyclic low molecular weight oligomeric poly(butylene terephthalate) resins have a low viscosity. Using such a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin as a starting material has the advantage that, due to its low viscosity, it is possible to compound the oligomeric material up to 85% by weight with a filler material such as silica, which is of special importance for the manufacture of filled electrical insulation parts. This is not possible with conventional poly(butylene terephthalate). The resulting filler containing polymer made from the cyclic oligomeric compounds further has mechanical and electrical properties that cannot be matched with conventionally filled poly(butylene terephthalate).
[0005] The low viscosity of the cyclic low molecular weight oligomeric poly(butylene terephthalate) resin gives also the possibility to manufacture large bulky electrical insulation parts with complex shapes, e.g. via injection molding, that cannot be manufactured directly with poly(butylene terephthalate). It further opens the possibility to impregnate reinforcements, like fiber fabrics or micatapes, conventionally used in electrical insulation, which is not possible with conventional thermoplastics.
[0006] The present invention is defined in the claims. Especially the present invention refers to an electrical insulation system based on poly(butylene terephthalate), optionally containing further additives, characterized in that said poly(butylene terephthalate) (i) has been obtained by polymerizing a cyclic low molecular weight oligomeric poly-(butylene terephthalate) resin.
[0007] The present invention further refers to an electrical insulation system based on poly(butylene terephthalate), optionally containing further additives, characterized in that said poly(butylene terephthalate) (i) has been obtained by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin and (ii) contains at least one filler material or a mixture of such filler materials in an amount of up to 85% by weight, calculated to the total weight of the insulation system.
[0008] The present invention further refers to an electrical insulation system based on poly(butylene terephthalate), optionally containing further additives, characterized in that said poly(butylene terephthalate) (i) has been obtained by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin and (iii) contains at least one hydrophobic compound or a mixture of such compounds, preferably an organopolysiloxane, in an amount of 0.1% to 10% by weight, calculated to the total weight of the insulation system.
[0009] The present invention further refers to an electrical insulation system based on poly(butylene terephthalate), optionally containing further additives, characterized in that said poly(butylene terephthalate) (i) has been obtained by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin, contains (ii) at least one filler material or a mixture of such filler materials in an amount of up to 85% by weight, and (iii) at least one hydrophobic compound or a mixture of such compounds, preferably an organopolysiloxane, in an amount of 0.1% to 10% by weight, each calculated to the total weight of the insulation system.
[0010] The present invention further refers to the use of poly-(butylene terephthalate), optionally containing further additives as defined herein, as an electrical insulation system, wherein said poly(butylene terephthalate) has been obtained by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin.
[0011] The present invention refers also to a method of making an electrical insulation system, optionally containing further additives as defined herein, which is characterized by (i) mixing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin with any additive, in any desired sequence, (ii) optionally applying the mixture obtained to the surface of a shaped article, and (iii) polymerizing the mixture.
[0012] Poly(butylene terephthalate) (PBT) is a known polymer. It is known to depolymerize PBT whereby a cyclic (also named macrocyclic) low molecular weight oligomeric poly(butylene terephthalate) resin of formula (I) is obtained:
[0013] In formula (I) n is 4 and m is an average number between 2 and 10, preferably between 2 and 5. The melting temperatures generally are in the range of from 140°C to 190°C, preferably in the range of from 160°C to 185°C, corresponding to melt viscosities at melting temperature within the range of about 35 mPa.s (SI-units) further decreasing with rising temperatures.
[0014] A catalyst is needed to polymerize the cyclic low molecular weight oligomeric poly(butylene terephthalate). Generally a specific tin or titanium catalyst, preferably stannoxane, butylchlorotin dihydroxide [BuSnCl(OH)2, CAS no.13355-96-9] or tetrakis(2-ethyl)titanate is used, whereby the cyclic ring opens and polymerizes, to yield a linear high molecular weight polymer without off-gassing and only a slight exothermic reaction caused by crystallisation. Such catalysts, the amounts and methods of using these catalyst, the polymerization conditions etc. are known in the art. High molecular weight PBT produced from cyclic oligomers has a melt temperature of about 220°C.
[0015] A typical basic formulation to be polymerized is for example composed of the cyclic oligomers of poly(butylene terephthalate) and the catalyst which initiates the polymerization reaction of the cyclic oligomers. The amount of catalyst added is preferably in the order of 0.2-0.5% by weight. More may be added, which is not critical. A filler material conventionally used in electrical insulation, may be added in concentrations as given herein.
[0016] Within the meaning of the present invention, the expression "has been obtained by polymerizing a cyclic low molecular weight oligomeric poly(butylene terephthalate) resin" includes also compositions wherein said cyclic low molecular weight oligomeric poly(butylene terephthalate) resin contains up to 40% by weight of cyclic low molecular weight oligomeric compounds of formula (I), or a mixture thereof, wherein n is 2 or 3, i.e. cyclic low molecular weight oligomeric poly(ethylene terephthalate) and cyclic low molecular weight oligomeric poly(propylene terephthalate), preferably within the range of 5% to 40% by weight and m having values between 2 and 10, preferably between 2 and 5.
[0017] According to an embodiment of the present invention the insulator system contains at least one filler material or a mixture of such filler materials. Filler materials for electrical isolation systems are known and are preferably selected from the group comprizing natural purified sands; silicon oxides and silicon hydroxides; aluminum oxides and aluminum hydroxides; titanium oxides and titanium hydroxides; zinc oxides and hydroxides; silicates, preferably sodium/potassium silicates, silicon aluminosilicates; mineral carbonates, preferably calcium-magnesium carbonate or calcium-silicon-magnesium carbonates; geopolymers, preferably trolites and/or zeolites based on aluminosilicates or other alkaline earth metals, glasses, mica, ceramic particles. Preferred are silicon oxides, aluminum oxides, titanium oxides, silicates, preferably silicon oxides (SiO2, Quarz), aluminum oxides and hydroxides, zinc oxide, sodium/potassium silicates and/or silicon aluminosilicates.
[0019] The mineral filler compound or the mixture of such compounds have a preferred average grain size (at least 50% of the grains) in the range of from about 1.0µm to 200µm, preferably in the range of from 1µm to 100µm, preferably in the range of from 5µm to 50µm, preferably in the range of from 5µm to 40µm, and especially in the range of from 5µm to 35µm.
[0020] The cyclic low molecular weight oligomeric poly(butylene terephthalate) resin, contains at least one filler material or a mixture of such filler materials in an amount of up to 85% by weight. The proportion of the filler material in the insulator system is preferably in the range of from 5% to 85% by weight, preferably in the range of from 40% to 80% by weight, and in particular in the range of from 60% to 80% by weight, preferably in the range of from 65% to 80% by weight, calculated to the total weight of the insulation system, i.e. polymer, filler and further additives.
[0021] In a further embodiment of the present invention the electrical insulation system contains at least one hydrophobic compound or a mixture of such compounds, especially for improving the self-healing properties of the electrical insulator. For this purpose the cyclic low molecular weight oligomeric poly(butylene terephthalate) resin is uniformly mixed with the hydrophobic compound or a mixture of said compounds, said hydrophobic compounds being selected from the group comprising flowable fluorinated or chlorinated hydrocarbons which contain -CH2-units, -CHF-units, -CF2-units, -CF3-units, -CHC1-units, -C(Cl)2-units, -C(Cl)3-units, or mixtures thereof; or a cyclic, linear or branched flowable organopolysiloxane. Said hydrophobic compound or said mixture of said compounds may be present in encapsulated form.
[0022] The hydrophobic compound preferably has a viscosity in the range from 50 cSt to 10,000 cSt, preferably in the range from 100 cSt to 10,000 cSt, preferably in the range from 500 cSt to 3000 cSt, measured in accordance with DIN 53 019 at 20°C.
[0023] Preferably the hydrophobic compound comprises a compound, or mixture of compounds, of the general formula (II):
in which
R independently of each other is an unsubstituted or chlorinated or fluorinated alkyl radical having from 1 to 8 carbon atoms, (C1-C4-alkyl)aryl, or aryl;
R1 independently at each occurrence has one of the definitions of R or R2, it being possible for two terminal substituents R1 attached to different Si atoms, being taken together to be an oxygen atom (= cyclic compound);
R2 has one of the definitions of R, or is hydrogen or a radical -(A)r-CH=CH2;
- A
- is a radical -CsH2s-, where
- s
- is an integer from 1 to 6;
- r
- is zero or one;
- m
- is on average from zero to 5000;
- n
- is on average from zero to 100;
[0024] Preferred is the compound of the formula (II), wherein R independently of each other is an unsubstituted or fluorinated alkyl radical having from 1 to 4 carbon atoms or phenyl; A is a radical -(CH2)-, m is on average from 20 to 5000; n is on average from 2 to 100; the sum of [m+n] for non-cyclic compounds being on average in the range from 20 to 5000, and the sequence of the groups -[Si(R)(R)O]- and -[Si(R1)(R2)O]- in the molecule being arbitrary.
[0025] Preferred is the compound of the formula (II), wherein R independently of each other is 3,3,3-trifluoropropyl, monofluoromethyl, difluoromethyl, or alkyl having 1-4 carbon atoms; A is a radical -(CH2)-; m is on average from 50 to 1500; n is on average from 2 to 20; the sum of [m+n] for non-cyclic compounds being on average in the range from 50 to 1500, and the sequence of the groups -[Si(R)(R)O]- and -[Si(R1) (R2)O]- in the molecule being arbitrary. Most preferred is a compound of the formula (II) wherein each R is methyl.
[0026] Preferred cyclic compounds of formula (II) are those comprising 4-12, and preferably 4-8, -[Si(R)(R)O]-units or -[Si(R1) (R2)O]-units or a mixture of these units.
[0027] Preferred further are compounds of the formula (II) comprising a cyclic, linear or branched polydimethylsiloxane which additionally contains vinyl groups or allyl groups, preferably a cyclic, linear or branched organovinylpolysiloxane. The hydrophobic compound may be encapsulated.
[0028] The hydrophobic compound is added to the cyclic low molecular weight oligomeric poly(butylene terephthalate) resin preferably in an amount of from 0.1% to 10%, preferably in an amount of from 0.25% to 5% by weigh, preferably in an amount of from 0.25% to 3% by weight, calculated to the weight of the oligomeric poly(butylene terephthalate).
[0029] The electrical insulation system according to the present invention may optionally contain further additives. Such additives are antioxidants, compatibilizers, plasticizers, tougheners. Such compounds are known.
[0030] Preferred uses of the insulation systems produced according to the present invention are high-voltage insulations for indoor and outdoor use, especially for outdoor insulators associated with high-voltage lines, as long-rod, composite and cap-type insulators, and also for base insulators in the medium-voltage sector, in the production of insulators associated with outdoor power switches, measuring transducers, leadthroughs, and overvoltage protectors, in switchgear construction, in power switches, dry-type transformers, and electrical machines, as coating materials for Transistors and other semiconductor elements and/or to impregnate electrical components. The present invention further refers to the electrical articles containing an electrical insulation system according to the present invention. The following examples illustrate the invention.
Example 1
[0031] A formulation was prepared from the following components: 100 parts cyclic low molecular weight oligomers of poly-(butylene terephthalate) (CBT®-XB3 from the Cyclics Corp.); 0.2 parts of the catalyst butylchloritin dihydride (Fascat® 4101, from Atofina Corp.); and 185 parts of dry silica powder (Millisil® B12 from Silhelco) having an average particle size (d50%) of 16µm.
- a) The oligomers of poly(butylene terephthalate) are melted at a temperature ranging from 130°C to 180°C and subsequently mixed with predried silica flower until an homogeneous mixture is obtained. The catalyst is then added so that the oligomers react and polymerize to form a high molecular weight poly(butylene terephthalate) thermoplastic.
- b) Alternatively, the catalyst is first compounded with the oligomers of polyethylene terephthalate prior to mixing with the silica flower.
[0032] The high molecular polymer produced has a melt temperature of about 220°C, which is higher than the processing temperature so that demolding is possible with little or no cooling. The mixing phase is carried out with a conventional mixer, a brabender, an extruder, or an injection molding machine. The filled mould is heated to about 180-200°C to allow the low molecular weight oligomers to react and form high molecular weight poly(butylene terephthalate). Alternatively, the reaction of the oligomers may take place prior to the filling of the mould. In this case the mixture is heated above 160°C prior to filling.
Example 2 (Comparative Example)
[0033] The properties of silica filled polybutylene terephthalate made from cyclic low molecular weight oligomers according to Example 1 are compared with the properties of silica filled anhydride-cured epoxies. The comparison of the properties are given in Figure 1.
Example 3 (Comparative Example)
[0034] The evolution of the dielectric constant at 50 Hz of silane treated silica filled (65 wt%) polybutylene terephthalate made from cyclic low molecular weight oligomers analogous to Example 1 is compared with silica filled anhydride-cured (65 wt% silane treated silica) epoxies. The comparison of the properties are given in Figure 2.
Example 4 (Comparative Example)
[0035] The evolution of the dielectric losses at 50 Hz of silane treated silica filled (65 wt%) polybutylene terephthalate made from cyclic low molecular weight oligomers analogous to Example 1 is compared with silica filled anhydride-cured (65 wt% silane treated silica) epoxies. The comparison of the properties are given in Figure 3.
[0036] Figure 1 (as Table 1): Comparison of properties of silica filled polybutylene terephthalate made from cyclic low molecular weight oligomers according to Example 1 with the properties of silica filled anhydride-cured epoxies.
1. Electrical insulation system based on poly(butylene terephthalate), optionally containing
further additives, characterized in that said poly(butylene terephthalate) has been obtained by polymerizing a cyclic low
molecular weight oligomeric poly(butylene terephthalate) resin.
2. Electrical insulation according to claim 1, characterrized in that said poly(butylene
terephthalate) contains at least one filler material or a mixture of such filler materials
in an amount of up to 85% by weight, calculated to the total weight of the insulation
system.
3. Electrical insulation according to claim 1, characterrized in that said poly(butylene
terephthalate) contains at least one hydrophobic compound or a mixture of such compounds,
preferably an organopolysiloxane, in an amount of 0.1% to 10% by weight, calculated
to the total weight of the insulation system.
4. Electrical insulation according to claim 1, characterrized in that said poly(butylene
terephthalate) contains at least one filler material or a mixture of such filler materials
in an amount of up to 85% by weight, and at least one hydrophobic compound or a mixture
of such compounds, preferably an organopolysiloxane, in an amount of 0.1% to 10% by
weight, each calculated to the total weight of the insulation system.
5. Electrical insulation according to any one of the claims 1-4, characterized in that the cyclic low molecular weight oligomeric poly(butylene terephthalate) resin corresponds
to the general,formula (I):
wherein n is 4 and m is an average number between 2 and 10, preferably between 2 and 5.
wherein n is 4 and m is an average number between 2 and 10, preferably between 2 and 5.
6. Electrical insulation according to any one of the claims 1-5, characterized in that the cyclic low molecular weight oligomeric poly(butylene terephthalate) resin contains
up to 40% by weight of a cyclic low molecular weight oligomeric compound of formula
(I) or a mixture thereof, wherein n is 2 or 3, preferably within the range of 5% by
weight to 40% by weight and m having values from 2 to 10, preferably between 2 and
5.
7. Electrical insulation according to any one of the claims 1-6, characterized in that the insulator system contains at least one filler material or a mixture of such filler
materials selected from the group comprizing natural purified sands; silicon oxides
and hydroxides; aluminum oxides and hydroxides; titanium oxides and hydroxides; zinc
oxides and hydroxides; silicates, preferably sodium/potassium silicates, silicon aluminosilicates;
mineral carbonates, preferably calcium-magnesium carbonate or calcium-silicon-magnesium
carbonates; geopolymers, preferably trolites and/or zeolites based on aluminosilicates
or other alkaline earth metals, glasses, mica, ceramic particles. Preferred are silicon
oxides, aluminum oxides, titanium oxides, silicates, preferably silicon oxides (Sio2, Quarz), aluminum oxides and hydroxides, zinc oxide, sodium/potassium silicates and/or
silicon aluminosilicates, which optionally are surface treated, preferably silanized.
8. Electrical insulation according to claim 7, characterrized in that the mineral filler
compound or the mixture of such compounds have an average grain size (at least 50%
of the grains) in the range of from about 1.0µm to 200µm, preferably in the range
of from 1µm to 100µm, and especially in the range of from 5µm to 50µm, preferably
in the range of from 5µm to 40µm, and especially in the range of from 5µm to 35µm.
9. Electrical insulation according to claim 7 or 8, characterized in that the mineral filler material or the mixture of the filler materials is present in
an amount of up to 85% by weight, preferably in the range of from 5% to 85% by weight,
preferably in the range of from 40% to 80% by weight, particular in the range of from
60% to 80% by weight, preferably in the range of from 65% to 80% by weight, calculated
to the total weight of the insulation.
10. Electrical insulation according to any one of the claims 1-9, characterized in that said electrical insulation system contains at least one hydrophobic compound or a
mixture of such compounds selected from the group comprising flowable fluorinated
or chlorinated hydrocarbons which contain -CH2-units, -CHF-units, -CF2-units, -CF3-units, -CHC1-units, -C(Cl)2-units, -C(Cl)3-units, or mixtures thereof; or a cyclic, linear or branched flowable organopolysiloxane,
wherein said hydrophobic compound optionally is present in encapsulated form.
11. Electrical insulation according to claim 10, characterized in that said hydrophobic compound has a viscosity in the range from 50 cSt to 10,000 cSt,
preferably in the range from 100 cSt to 10,000 cSt, preferably in the range from 500
cSt to 3000 cSt, measured in accordance with DIN 53 019 at 20°C.
12. Electrical insulation according to claim 10, characterized in that said hydrophobic compound corresponds to the general formula (II):
in which
R independently of each other is an unsubstituted or chlorinated or fluorinated alkyl radical having from 1 to 8 carbon atoms, (C1-C4-alkyl)aryl, or aryl;
R1 independently at each occurrence has one of the definitions of R or R2, it being possible for two terminal substituents R1 attached to different Si atoms, being taken together to be an oxygen atom (= cyclic compound);
R2 has one of the definitions of R, or is hydrogen or a radical - (A)r-CH=CH2;
in which
R independently of each other is an unsubstituted or chlorinated or fluorinated alkyl radical having from 1 to 8 carbon atoms, (C1-C4-alkyl)aryl, or aryl;
R1 independently at each occurrence has one of the definitions of R or R2, it being possible for two terminal substituents R1 attached to different Si atoms, being taken together to be an oxygen atom (= cyclic compound);
R2 has one of the definitions of R, or is hydrogen or a radical - (A)r-CH=CH2;
A is a radical -CsH2s - , where
s is an integer from 1 to 6;
r is zero or one;
m is on average from zero to 5000;
n is on average from zero to 100;
the sum of [m+n] for non-cyclic compounds being at least 20, and the sequence of the groups -[Si(R)(R)O]- and - [Si(R1) (R2)O]- in the molecule being arbitrary.13. Electrical insulation according to claim 12, characterized in that a compound of the formula (II) is used, wherein R independently of each other is
an unsubstituted or fluorinated alkyl radical having from 1 to 4 carbon atoms or phenyl;
A is a radical -(CH2)-, m is on average from 20 to 5000; n is on average from 2 to 100; the sum of [m+n]
for non-cyclic compounds being on average in the range from 20 to 5000, and the sequence
of the groups - [Si (R) (R) O] - and - [Si (R1) (R2)O]- in the molecule being arbitrary.
14. Electrical insulation according to claim 12, characterized in that a compound of the formula (II) is used, wherein R independently of each other is
3,3,3-trifluoropropyl, monofluoromethyl, difluoromethyl, or alkyl having 1-4 carbon
atoms; A is a radical -(CH2)-; m is on average from 50 to 1500; n is on average from 2 to 20; the sum of [m+n]
for non-cyclic compounds being on average in the range from 50 to 1500, and the sequence
of the groups - [Si (R) (R) O] - and -[Si(R1) (R2)O]- in the molecule being arbitrary, preferably wherein each R is methyl.
15. Electrical insulation according to claim 12, characterized in that the compound of the formula (II) is a cyclic compound comprising 4-12 and preferably
4-8 -[Si(R)(R)O]-units or -[Si(R1)(R2)O]-units or a mixture of these units, preferably a cyclic, linear or branched polydimethylsiloxane
which additionally contains vinyl groups or allyl groups, preferably a cyclic, linear
or branched organovinylpolysiloxane, said silanes optionally being encapsulated.
16. Electrical insulation according to any one of the claims 12-15, characterized in that the compound of the formula (II) is added in an amount of from 0.1% to 10%, preferably
in an amount of from 0.25% to 5%, preferably in an amount of from 0.25% to 3% by weight,
calculated to the weight of the oligomeric poly(butylene terephthalate).
17. Electrical insulation according to any one of the claims 1-16, characterized in that said electrical insulations are high-voltage insulations for indoor and outdoor use,
preferably for outdoor insulators associated with high-voltage lines, as long-rod,
composite and cap-type insulators, and also for base insulators in the medium-voltage
sector, insulators associated with outdoor power switches, measuring transducers,
leadthroughs, and overvoltage protectors, in switchgear construction, in power switches,
dry-type transformers, and electrical machines, coating materials for transistors
and other semiconductor elements and/or to impregnate electrical components.
18. Electrical articles containing an electrical insulation system according any one of
the claims 1-17.
19. Method of making an electrical insulation system as defined in any one of the claims
1-16, characterized by (i) mixing a cyclic low molecular weight oligomeric poly-(butylene terephthalate)
resin in any desired sequence with any additive which is present, (ii) optionally
applying the mixture obtained to the surface of a shaped article, and (iii) polymerizing
the mixture.